Dendrimers up to the fourth generation were successfully prepared via the divergent growth strategy using a combination of thiol-ene "click" chemistry and traditional esterification reactions. The thiol-ene reactions were conducted under solvent-free, ambient conditions at room temperature by irradiating with UV light. The fourth-generation dendrimers were subsequently functionalized with carboxylic acid, pyrene, and Fmoc-protected cysteine moieties via thiol-ene reactions.